Treatment of hydrocarbon distillates



'those of normal and isomeric character.

Patented May 9, 1944 UNITED 8 Claims.

This invention relates to the treatment of hydrocarbon distillates of approximate gasoline boiling range produced from petroleum, and is more specifically concerned with the catalytic refining of such distillates under hydrogenating conditions and under the influence of selective catalysts to improve their antiknock properties although the treatment has other desirable effects in that color, odor, and boiling range are improved.

Straight run gasolines and naphthas produced by simple non-cracking distillation of crude petroleums consist almost entirely of naphthene and paraflln hydrocarbons in varying propor tions, the distribution and characteristics of these groups of hydrocarbons determining generally the antiknock value of the gasoline. In the case of the naphthene hydrocarbons, those having 5, 6, and 7 carbon atom in the ring may be present, and of paraflin hydrocarbons, both The most desirable hydrocarbons in motor fuels and particularly in aviation fuels have been shown to be the more highly branched iso-parafiins boiling within the range of approximately 100-400 F., the reference standard iso-octane, 2,2,4-trimethyl pentane being a case in point. Owing to the generally low antiknock values of straight run gasolines except possibly some of those from the California and Gulf Coastal fields, they are quite uniformly subjected to so-called reforming processes which may involve simple thermal cracking or treatments employing selected catalysts to direct the course of the conversion reactions toward higher antiknock values with improved yields of gasoline boiling range product. The present process is a contribution to the art of reforming gasolines employing special catalysts and conditions of operation in respect to temperature, pressure, times of reaction, hydrogen atmosphere, and stage operation.

In one specific embodiment the present invention comprises a method for reforming gasolines of relatively low antiknock value to increase the -antiknock value thereof which consists in subjecting the gasoline mixed with hydrogen to contact with selected hydrogenating catalysts at temperatures of the order of 475-525" C. (890-980 F.) pressures of the order of 100-300 pounds per square inch and liquid space velocities of approximately 0.5 to 20 in a primary stage, and further subjecting the products from the primary stage in the presence of hydrogen STATES PATENT TREATMENT OF nYpRocARBc-n DISTILLATES William J. Mattox, Chicago, Ill., assignor to Universal Oil Products Company, Chicago, 11]., a corporation of Delaware No Drawing. Application October 17, 1940, Serial No. 361,583

I At the same time there may be some dehydro-i to further contact with dehydrogenating oatalysts at temperatures of the order of 525-600 hydroreforming of low antiknock value straight run gasolines are obtainable when the treatment is conducted in stages under conditions of increased severity in respect to dehydrogenation than when single stage operation employing in-'- termediate conditionsis used. While it is not intended to limit the invention by any exposition of theoretical reaction mechanisms which might account for the improved effects observed, there is evidence to support the theory that the un-; expected results obtained may be due to the de structive hydrogenation of 5-carbon atom ring naphthenes under the conditions employed in the first stage of the process,-these compoundsbeing converted into iso-parafllns by hydrogena tion reactions involving the opening of the ring.

genation of 6-carbon atom ring naphthenes to aromatics. There is also experimental evidence to indicate that when catalysts and conditions suitable to dehydrogenate and cyclize aliphatic hydrocarbons are employed on mixtures of gasoline hydrocarbons comprising both naph-j thenes and paraffin that the five-carbon atomf naphthenes present are extensively decomposed with the liberation of large amounts of carbori and gas. Thus, if a single stage method of treatment is employed in the catalytic reforming of many gasolines containing both five carbon atom ring naphthenes and aliphatic hydrocar-T bons, there is a rapid deposition of carbonaceous materials on the catalyst even under the in-- fluence of a hydrogenating atmosphere so that frequent reactivations are necessary with a consequent decrease in the overall production of the equipment. Later examples will be introducec to indicate the advantages of operating in the present preferred step-wise manner rather than in a single stage. Advantages may also be gained at times in operating in a succession 01 more than two stages with conditions modified along the line of flow so that dehydrogenation and dehydrocyclization reactions are progres-f sively favored.

When it has been indicated that rather nar row temperature andpressure ranges are gen-i erally preferable in the two stage operation, it is not intended to limitgthe invention in accordance with these ranges on account of the 8X1 tremely variable character of the gasoline. which may be subjected to treatment. a primary stage, temperature as low as 200 C, and as high as 600 C. may sometimes be used and pressures may vary from -1000 pound per square inch. In the second stage tempera tures from 450 to 650 C. may be used and pres sures from substantially atmospheric to ap-. proximately 200 pounds per square inch. Th general conditions for successful operation are that the set of conditions employed in the second Thus ir stage (including catalysts) tend to induce a greater degree of dehydrogenation and/or dehydrocyclization rather than hydrogenation or in other words to shift the hydrogenation-dehyized, mixed with a controlled amount of hydrogen, and introduced into a reactor containing a granular hydrogenation-dehydrogenation catalyst, the reactor being maintained at a given drogenation equilibrium in the direction of the 5 temperature and pressure, usually determined by latter reaction. small scale experiments. The rate of flow is ad- As a further means of controlling the relative .l increase the Octane number of the hydrogenating-dehydrogenating equilibria which charge to only-a limited e t o e p n to differentiate the first and second stages, it is coma minimum deposition of carbon. the further prised within the scope of the invention to emr se being r v f r the second stage of opploy considerable variations in space or mass eration. velocities as related to temperature in the two f r t e fi t sta e of treat ent the tota stages of the process. The selection of the proper P d ts y be P e directly to y o amass velocity, which in continuous apparatus tion treatment or may be subjected to intermemay be varied by varying the diameters of reacdiate fractionation with the separation of gasetion chambers in respect to their length, will ous and liquid conversion products and the sehave a definite effect in further reducing carbon lection of individual cuts for further treatment. deposition as will be indicated in later examples. In general the operation of the second stage and The following tabulation indicates three possithe apparatus employed therefor will be genble alternative, modes of operation employing a erally the same as that of the first stage and two-stage process to effect optimum results in consists of a vaporizer if the liquid products have the increasing of antiknock value of gasolines by been condensed, or simply a further section of two-stage hydroreforming operations. reactor containing catalyst in case the total prod- Alf Temp Molal emotive processes Stage lressure,lbs. per square inch cc Feed rate hygiggen 1 High pressure loo-1,000; 2o0550 0.5 to20S. v. 0.5-40 2 Ann-200-.. BOO-650 0.1 tofi s.v. 0.5-40 zoo-reg High s.v. 2- 0.5-40 88mm ::}200-550' Highmassvelocity 0.5-40

X Hourly liquid space velocity.

It is noted that in general the pressure is higher ucts have been passed to further treatment within the first stage of operation, that the temperaout fractionation. After the second, or final ture is lower and that the space velocity is highstage, in case more than two are employed, the er, while the hydrogen ratio may be varied to acproducts are fractionated to recover reformed commodate the needs of different stocks. I gasoline fractions and hydrogen-containing gases A considerable number of catalysts may be which maybe recycled for further use. successfully employed in the two stages of the Whether the first stage of operation will reprocess although not with exactly equivalent require the extraction of heat to maintain the temsults and either the same type of catalyst may perature due to hydrogenation of 5-carbon atom be used in the two stages or different catalysts ring naphthenes or will require the addition of of varying activity. Thus a distinctly hydrogenheat due to dehydrogenation of B-carbon atom ating catalyst such at nickel, cobalt, or platinum ring naphthenes will in general depend on the may be used in the primary stage while essenrelative amounts of these two types of naphtially dehydrogenating catalysts including the thenes. oxides of the left-hand members of the groups Owing to the fact that there is generally alower V and VI of the peri di -D y O rate of carbon deposition in the first stage of the pports-in the second ry stage. It is further process, it is frequently possible to utilize the comprised within the scope of the invention to' catalytic material of the first stage after a period employ t e sa e cata yst n oth S a s, While of operation as a catalyst for the second stage depending p the va ation in operating 001 since its activity in respect to dehydrogenation unditions to effect the desired results. Any of the der the more severe conditions or the second stage C a y s y be supp t d 011 ch relatively may be sufficiently high while it has depreciated active carriers as the oxides of alumi u to an undesirable extent for the first stage hydroesi Zine, Silica, siliceous and generally regenation reactions. It is obvious that this offer: fractory materials, including clays, either raw or advantages as to capacity of apparatus and than acid treated, fullers earth OI synthetically prenumerous flows can be devised using parallel re. pared S a-a DO S- The Selection action chambers to take advantage of this feature of the best catalysts for use in the Successlve The following examples are introduced to shov stages of the treatment will be determined by the the type f results obtainable by the use of m, characteristics of the gasoline to be reformedpresent process, although not with the intent o and the results desired. limiting its proper scope.

With respect to the hydrogen-hydrocarbon ratios, these will also be varied to suit the needs EXAMPLE I of different situations with respect to charge and results desired but generally no additional hy- In a first stage a 33.5 octane number, 198405 drogen will be employed in the secondary or F. boiling range ,Mid-Continent naphtha wa 1ater tages. 1 passed with 4 moles of added hydrogen over a1 Various types of apparatus and modes of op- 8% chromium sesquioxide-92% alumina catalys eration may be employed within the scope of the at 500 C., 2 liquid space velocity, and 300 pound invention. In one of the simpler modes of oppressure for six hours. The liquid recover eration, a low octane number gasoline is vapor amounted to 97.0 volume per cent and had a octane number of 40.5. Only 0.005% of the charge was converted to carbon on the catalyst.

The hydrocarbon recovered from the above first stage was passed with 4 moles of hydrogen over a portion of the above 8% chromium sesquioxide catalyst at 550 0., 0.5 space velocity, and 50 pounds for six hours. The volume of liquid recovered amounted to 83.5% of the charge to the second stage or 81.0% of the charge-to the first stage. The octane number of the reformed naphtha from this stage was 76.0. Carbon formation amounted to 1.0% of the charge. The overall results of these two operations are summarized in the following table. Data from a run made under the same operating conditions as for the above second stage but without the first stage of the operation are also included in the table.

From the above data the marked decrease in carbon formation will be noted. Although the octane number of the gasoline from the two-stage operation is 4 octane numbers lower than resulted from the one stage, the yield is higher. Producing a '76 octane number gasoline in a one-stage operation gave 1.5% carbon, so that by either comparison the carbon formation for a similar degree of conversion has been greatly reduced by the operation described. EXAMPLE H y The first stage of this typical treatment was conducted in the same manner as Example I.

A portion of the hydrocarbons recovered from the first stage was passed with 2 moles of hydrogen over. an 8% C1203-92% A1203 catalyst at 550 ii, 0.5 space velo'city,and 50 pounds for six hours. it will be noted that this-operation differs from Example I in that only 2 moles of hydrogen are used. The overall yields of these two operations are summarized in the table following. Data from a one-stage run made at 550 C., 0.5 space velocity, 50 pounds pressure and with 2 moles of hydrogen are included in the table for comparisom Two-stage One-stage lion number .1 a--i034 981 Yields, per cent oi charge:

Gasoline, vol. per cent 75.0 76. 2 Gasoline, wt. per cent 77. 7 78. 8 Gas, uncondensed, wt 20.9 19.

P B 1. 2 Carbon 2. 13 3. 95 Unaccounted +0. 7 +3. 5 Carbon deposition, wt. per cent cat 5.1 8.8 Octane number, M. M 80. 5 80. 0

In this two-stage operation a slightly higher octane number, 80.5, gasoline was produced-than by the one-stage and with about the same yield, carbon formation however being only about one-half as much as in the one-stage operation. However, the results obtained in Example I in which 4 moles of added hydrogen were used in the second stage are better in view of the 0.98% carbon.

EXAMPLE III In this example the two stages were carried out as a single operation, the two furnaces used being controlled separately. The total productsfrom the first were passed through a reducing valve directly to the second without any intermediate separation. In this run the temperature in the first stage was 475 C., while the second was held at 550 C. A 78 vol. yield of 80 octane number gasoline was obtained with only 1.9% carbon. Producing an 80 octane number gasoline in a one stage operation, with approximately 4 moles of exit hydrogen (1.93 mols added hydrogen) the yield was only 76 vol. and the carbon deposit on the catalyst 3.95 wt. of the charge. Thus, as shown in this example, by reforming straight run naphtha according to the procedure described in this invention carbon formation has been greatly reduced.

EXAMPLE IV By reforming a -405 F. boiling range Mid- Continent naphtha according to the procedure described above the following results have been obtained:

Catalyst: 8% Gino s-92% A12O3,' pellets Pressure: 50 pounds, both stages Temperature: 525 C., 1st stage; 550 0., 2nd

stage Hydrogen added: 4 mols/mol. of charge Run number Stage number Space veL, each stage. Space vel., overall.. Gasoline yield, vol.

per cent Octane number,

M. M Carbon, wt. per cent of cbg.: Two stage. (Carbon, wt. per cent of charge, for same octane number by one-stage process with 4 mols. added hydrogen) Catalyst: 8% smo -92% A1303, Va" pellets in both stages Pressure: 50 pounds, in both stages Temperature: 550 C. in. both stages Run number Hydrogen added,

molsJmol. chg 4 4 8 8 Stage number 1 2 l 2 l 2 Space veL, each stage 4.04.0 2. 7-i-0. 09 2.70-0.68 Space velocity overall"... 0.80 0.55 0. 54 0. 45 Gasoline yield, vol. per

cent oichg 81.2 72.5 80.2 77.0 Octane number, M. M. 77.5 82.0 81. 0 81. 0 Carbon, wt. per cent of chg.: Two stage 1.1 2. 3 0. 5 (One stage-4 mole hydrogen) (1.7) (2.8) 1.3) 1.3)

l 8 mols hydrogen. I One-stage run.

A. considerable reduction in carbon formation was obtained in these experiments, the reduction amounting to over 60% in run No. 3. A onestage run, No. 4, is included in the above table for comparison.

I claim as my invention:

1. A process for improving the antiknock characteristics of hydrocarbon distillates comprising gasoline fractions containing naphthenes having five carbon atoms in the ring, which comprises subjecting the hydrocarbon distillate to the action of hydrogen at hydrogenating conditions of temperature, pressure and space velocity, and in the presence of a hydrogenating catalyst to convert said naphthenes into open-chain, aliphatic hydrocarbons, and subjecting the resultant conversion products to reforming in the presence of a dehydrogenating catalyst.

2. The process of claim 1 further characterized in that the reforming step is accomplished at a higher temperature than that maintained in the first mentioned conversion step.

n 3. The process of claim 1 further characterized in that the reforming step is carried out in the presence of hydrogen.

4. The process of claim 1 further characterized in that the reforming step is operated at a pressure lower than that employed in the first mentioned conversion step. t

5. The process of claim 1 further characterized in that the hydrogenating catalyst comprises nickel and the dehydrogenating catalyst comprises alumina and chromia. I 6. A process for improving the antiknock characteristics of hydrocarbon distillates comprising gasoline fractions containing naphthenes having five carbon atoms in the ring, which comprises subjecting the hydrocarbon distillate to the action of hydrogen at hydrogenating conditions of temperature, pressure and space velocity, and in the presence of a hydrogenating catalyst to convert said naphthenes into open-chain, aliphatic hydrocarbons, and subjecting the resultant conversion products, including the unused hydrogen from the hydrogenating step, to the action of a dehydrogenating catalyst at reforming conditions of temperature and pressure to produce gasoline of high octane rating.

7."A process for reforming gasoline of relatively low octane number to improve the octane number thereof which comprises subjecting the vapors of said gasoline mixed with hydrogen at a temperature of from about 475 to about 525 C.,t-a pressure of from about 100 to about 300 pounds per square inch and at a liquid hourly space velocity of from about 0.5 to about 20 to contact in a first stage with a catalyst consistingfof nickel deposited on kieselguhr, effective in converting naphthenes to parafllns by hydrogenation, and in the second stage at a temperature from about 525' to about 600 ,C., a pressure of from about atmospheric to about 100 pounds per square inch and a liquid hourly space velocity of from about 0.1 to about 10 to contact with a catalyst consisting of molybdenum oxide deposited on alumina effective in dehydrogenating aliphatic hydrocarbons to cyclic hydrocarbons, the space velocity in said second stage being lower than in said first stage.

8. A process for reforming gasoline of relatively low octane number to improve the octane number thereof which comprises subjecting the vapors of said gasoline mixed with hydrogen at a temperature of from about 475 to about 525 C., a pressure of from about 100 to about 300 pounds per square inch and at a liquid hourly space velocity of from about 0.5 to about 20 to contact in a first stage with a catalyst consisting 'of nickel deposited on kieselguhr, effective in converting naphthenes to parafiins by hydrogenation, and in the second stage at a temperature from about 525 to about 600 C., a pressure of from about atmospheric to about 100 pounds per square inch and a liquid hourly space velocity of from about 0.1 to about 10 to contact with a catalyst consisting of vanadium oxide deposited on alumina. effective in dehydrogenating aliphatic hydrocarbons to cyclic hydrocarbons, the space velocity in said second stage being lower than in said first stage.

WILLIAM J. MATTOX. 

